Hydrogenation catalyst composition consisting of aluminum, copper and cadmium



United States Patent 3 412,042 HYDROGENATION CATALYST COMPOSITION CONSISTING OF ALUMINUM, COPPER AND CADMIUM Shiro Kudo, Seiichi Yada, and Takayoshi Yamauchi, Sakai-ski, Japan, assignors to Kyowa Hakko Kogyo (10., Ltd., Tokyo, Japan, a corporation of Japan No Drawing. Continuation-impart of application Ser. No. 340,485, Jan. 27, 1964, which is a continuation-in-part of application Ser. No. 223,249, Sept. 12, 1962. This application June 23, 1965, Ser. No. 466,435 Claims priority, application Japan, Sept. 22, 1964, 39/ 53,896 8 Claims. (Cl. 252-463) ABSTRACT OF THE DISCLOSURE Raney type catalysts prepared from ternary alloys of copper-cadmium-aluminum. The leached alloy catalysts may be activated by heating said leached alloy catalysts at a temperature from 250 to 350 C. under a hydrogen gas stream or in an inert atmosphere. The catalysts are highly selective, and produce increased yields of OQfi-llllsaturated carbonyl compounds. The catalysts also have utility in the production of unsaturated higher aliphatic alcohols by hydrogenating either unsaturated fatty acids or unsaturated fatty acid esters.

This application is a continuation-in-part of copending application Ser. No. 340,485, filed Jan. 27, 1964, now abandoned, which is in turn a continuation-in-part of application Ser. No. 223,249, filed Sept. 12, 1962 and now abandoned.

The present invention embodies two aspects, both directed to new catalysts, their production, and their use.

In the first aspect, the catalyst is a Raney copper cadmium catalyst prepared from a ternary alloy of about 30 to 60 percent by weight of aluminum and the remainder copper and cadmium. The cadmium content is about 4 to percent by weight of said remainder, and the cop per content is about 96 to 85 percent by weight of said remainder.

In the second aspect, the catalyst is a Raney copper cadmium catalyst prepared from a ternary alloy of about to 60 percent by weight of aluminum, the remainder being copper and cadmium. The cadmium content is about 1 to slightly less than 4 percent by weight of said remainder, and the copper content is from a little more than 96 to about 99 percent by weight of said remainder.

Said catalysts are used in the production of a,B-unsaturated alcohols by hydrogenating a e-unsaturated aldehyes and by hydrogenating a,fi-ketones. Said catalysts are also useful in the production of unsaturated higher aliphatic alcohols by hydrogenating either unsaturated fatty acids or unsaturated fatty acid esters.

In hydrogenating a ti-unsaturated aldehydes and ketones using an ordinary hydrogenation catalyst, it is very difficult to produce the corresponding unsaturated alcohol in a satisfactory yield, since the double bond in the unsaturated aldehyde or ketone is more easily hydrogenated than the carbonyl group.

The present catalysts are hydrogenation catalysts which have a high degree of specificity and which permit the production of ugh-unsaturated alcohols from o e-unsaturated carbonyl compounds through selective hydrogenation with a high yield.

Thus, an object of the invention is to provide novel active hydrogenation catalysts to be used for the production of a e-unsaturated alcohols by selective hydrogenation of a, 8-unsaturated carbonyl compounds. Another object of the invention is to provide a method for prepar- 3,412,042 Patented Nov. 19, 1968 ing such catalysts to be used for the production of afi-UlllSatlll'BIed alcohols by selective hydrogenation of cl e-unsaturated carbonyl compounds.

A further object of this invention is the catalytic hydrogenation of unsaturated fatty acids and of unsaturated fatty acid esters to produce unsaturated higher aliphatic alcohols. It is also an object of this invention to conduct the hydrogenation in an economically feasible manner with small amounts of catalyst. A still further object of the invention is to employ a catalyst which can be easily and essentially completely separated from the alcohols produced and which can be effectively reused without revitalization.

Other objects are apparent from the following description.

The invention, in the first aspect, provides a method for preparing a catalyst used for the production of 11,5- unsaturated alcohols by hydrogenation of a e-unsaturated carbonyl compounds in gaseous phase, which comprises melting a mixture of aluminum, copper and cadmium containing 30 to 60% by weight of aluminum, and the remainder of copper and cadmium, the proportion of cadmium in the remainder being 4 to 15% by weight, to form a molten ternary alloy, rapidly cooling and then pulverizing said alloy, treating said pulverized alloy with an aqueous alkali solution, washing said alloy with water and removing the resultant Raney copper cadmium catalyst composition. A catalyst composition is obtained which is effective in the hydrogenation process of this invention. It is highly selective and will accomplish the objects of the invention. The selectivity of the catalysts may be increased as well as the yield of unsaturated alcohol by an additional treatment. This treatment comprises heating said catalyst at a temperature from 250 to 350 C. under a hydrogen gas stream or in an inert atmosphere.

The resultant catalyst composition is a Raney copper cadmium catalyst which possesses a high degree of selectivity. It is composed essentially of 1 to percent by weight of aluminum and a remainder of cadmium and copper with cadmium being 4 to 15 percent by weight of this remainder. The surface area of the catalysts ranges from 5 to 70 square meters per gram (m. /g.). The composition which is preferred is that which is prepared from ternary alloy containing 40 to 50 percent by weight (wt. percent) of aluminum, 3 to 7 wt. percent cadmium and 43 to 57 wt. percent copper.

The invention, in the second aspect, provides a method for preparing a catalyst useful for producing a,;3-unsatu rated alcohols by hydrogenating c p-unsaturated aldehydes and/ or ketones. Said catalyst is also useful in the production of unsaturated higher aliphatic alcohols by hydrogenating either unsaturated fatty acids or unsaturated fatty acid esters.

The method described supra is also useful for the preparation of the second catalyst except that the starting mixture contains from 30 to 70% by weight of aluminum, the remainder being cadmium and copper. The cadmium content is about 1 to less than 4% by weight of said remainder and the copper content is from a little more than 96 to about 99% by weight of said remainder. After melting this mixture, to form a molten ternary alloy, rapidly cooling and then pulverizing said alloy, treating said pulverized alloy with an aqueous alkali solution, washing said alloy with water, there is formed a Raney copper cadmium catalyst composition containing 1 to percent by weight of aluminum and a remainder of cadmium and copper, with cadmium being 1 to less than 4 percent by Weight of this remainder. The surface area of the catalyst ranges from 5 to square meters per gram (m. /g.).

German Patent No. 858,247 mentions a method of carrying out a hydrogenation reaction by use of a metal capable of hydrogenation (for example, copper, nickel and iron) along with cadmium. In this method, cadmium and other metals capable of hydrogenation (for example copper) are used after converting their nitrate or acetate to hydroxide by an alkali, followed by calcination and reduction, or after mixing cadmium hydroxide with the metal in oxide form, followed by calcination and reduction. This patent recommends a reaction pressure higher than 20 atmospheres, particularly from 100 to 300 atmospheres.

US. Patent No. 2,763,696 discloses another method of carrying out the reaction. In this method a precipitated catalyst prepared from cadmium and a metal belonging to the copper group is used. The reaction temperature ranges from 210 to 280 C., and the reaction pressure from 20 to 50 atmospheres.

Although catalysts prepared from cadmium, combined with metals having hydrogenating ability, may have selectivity in this reaction, prior art catalysts as disclosed in the above-noted patents have unavoidable disadvantages in that the hydrogenation is conducted at high temperatures and at high pressures because of the insufiicient activity of the catalysts.

The present catalysts make possible the desired hydrogenation at ordinary pressure, i.e. at about atmospheric pressure, and at a lower reaction temperature than known catalysts. These catalysts are prepared from an aluminumcopper-cadmium ternary alloy by treating with an alkali as set forth above.

By additionally heat-treating the Raney copper cadmium catalysts of this invention at a prescribed temperature, the selectivity of the catalysts is increased. The heattreated catalysts give a remarkably increased'yield of unsaturated alcohols, but give a little lower conversion of the reaction, as compared with the merely alkali-treated catalyst. However, yield and conversion of the catalysts of the invention are much higher than those of known catalysts, as seen in the examples.

The Raney copper cadmium catalysts of the invention are prepared, for example, as follows. Melting the alloy may be effected in a graphite crucible using an electrofurnace. For easier preparation of the ternary alloy of a definite composition, it is convenient preliminarily to prepare binary alloys of aluminum-copper and cadmiumcopper of definite compositions, and then to fuse these mother alloys together to make the ternary alloy. The molten alloy is well agitated with a silica rod, poured out from the graphite crucible onto a floor to form a plate 2 to 3 mm. thick, cooled by water, and crushed to 2 to 3 mm. particles.

The alloy particles are treated with an aqueous alkali solution, such as sodium or potassium hydroxide solution, washed with water, heated, and then used for the hydrogenation. Upon the alkali-treatment, a greater part of the aluminum is dissolved out, as in the alkali treatment of usual Raney-type catalyst.

The heat-treatment to increase the selectivity of the catalysts of the invention is effected at a temperature of from 250 to 350 C., preferably from 270 to 300 C., under a hydrogen stream. The heat-treatment under an inert gas, such as nitrogen, has a similar effect on activity and selectivity.

The catalysts prepared according to the method of the invention are used for the gaseous phase selective hydrounsaturated alcohols. Particularly, the catalysts are suitable for the hydrogenation of u,B-unsaturated carbonyl compounds having 3 to 12 carbons, especially 3 to 8 carbons, to the corresponding a,fi-unsaturated alcohols. Examp es of the a,/3-unsaturated carbonyl compounds are acrolein, crotonaldehyde, a-methylacrolein, 2-ethyl-penten-2-a1-l, 2-ethyl-hexen-2-al-1, mesityl oxide, methyl vinyl ketone, methyl propenyl ketone, methyl isopropenyl ketone, methyl pentenyl ketone, and the like, which yield al yl alcohol, crotyl alcohol, 2-methyl-propen-2-o1-1, 2-ethylpenten-Z-ol-l, 2-ethyl-hexen-2-o1-l, 2-methyl-penten-2-o1- 4, buten-1-ol-3, penten-2-ol-4, 2-methyl-buten-l-0l-3, hepten-3-o1-2, and the like, respectively.

The method of the invention is more fully described with reference to the working examples. The reaction tube employed for the hydrogenation in the examples is 18 mm. (millimeters) inner diameter and 400 mm. length, the middle portion of which is filled with 20 cc. (cubic centimeters) of catalyst. In Examples 1 to 8 vaporized a,;8-unsaturated aldehyde or ketone and hydrogen are supplied from the top of the reaction tube at a mol ratio of 1:12. The composition of the collected reaction product is determined by combination of gas chromatograph and chemical analysis. The melting process of alloys in Examples 2 through 8 is similar to that mentioned in Example 1. The condition and processes of alkali-treatment and washing of the catalyst after the treatment, and way of catalyst filling, in Examples 2 through 8, are wholly the same as in Example 1. The term, conversion, used in the examples means percentage of a,,B-unsaturated aldehyde or ketone converted to other substance, based upon the same charged to the reaction tube. The term, yield, means percentage of objective v e-unsaturated alcohol based upon the a,fl-unsaturated aldehyde or ketone converted to other substance. The term, L.S.V., namely, liquid space velocity, means volume at 20 C. of a,fi-unsaturated aldehyde or ketone supplied to a unit volume of catalysts per hour. The alloy composition is expressed by weight ratio. The reaction temperature is indicated in degrees centigrade and the reaction pressure in absolute kg./cm.

EXAMPLE 1 Melt 176 g. (grams) of binary alloy block of aluminum-copper (40:48 by weight) in a No. 2 graphite crucible heated to about 700 C. by an electro-furnace. Add 24 g. of binary alloy block of cadmium-copper (1:1 by weight) thereinto under agitation. Agitate the resulting molten alloy well with a silica rod .and pour out onto a floor to make a plate of 2 to 3 mm. (millimeters) thickness. Cool said alloy rapidly with water. After cooling, crush the alloy into 2 to 3 mm. particles.

Submerge fifty grams of the alloy in 1 kg. (kilogram) of aqueous 5% caustic soda solution at to 101 C. for 2 hours, whereby a greater part of the aluminum in the alloy is dissolved out. After removal of the alkali solution, continually wash the alloy with 3 liters of water under a hydrogen stream of 50 to 100 mm. Hg, and then fill a reaction tube with the catalyst from the top under a hydrogen stream.

The following Table 1 shows the results of hydrogenation of crotonaldehyde by use of the resulting catalyst, and those by use of catalyst obtained by heat-treatment of the filled catalyst at 275 C. under a hydrogen genation of ego-unsaturated carbonyl compounds to (1, 3- 65 stream for 3 hours.

TABLE 1 Catalyst Reaction Liquid Alloy Composl- Pressure Reaction space Conversion Yield tron (wt. percent) Composition Surface Treatment (kg/cm. Temperature velocity (percent) (percent) CuzOdzAl (wt. percent) Area abs.) C.) (l./l. hr.)

Cu:Cd:Al /gJ l 0. 66 2. 0 28. 3 19. 0 275 C., 3 hrs. under H2--- 1 0. 55 12. 6 80. 9 54.0:6.0:40.0 72.9:8.1:19.0 1 225 0. 60 26. 8 79. 0 h I 1 125 0. 60 35. 3 15. 0 l9. 3 Without heating l 175 0. 58 48. 9 32. 3 l 1 225 0. 54 55. 6 59. 8,

with those of a binary precipitated catalyst of coppercadmium on diatomaceous earth. The latter binary catalyst is prepared by a known method, namely: caustic soda is added to an aqueous solution containing copper nitrate and cadmium nitrate, thereby co-precipitating a copper hydroxide and cadmium hydroxide mixture, which is then mixed with the carrier, dried at 110 to 115 C., calcined at 400 C. for 4 hours in air, and reduced at 300 C. for 3 hours.

EXAMPLE 3 In Table 3, activities and selectivities of the coppercadmium binary catalyst on diatomaceous earth, as prepared in Example 2, are compared with those of Raney copper cadmium catalysts in the hydrogenation of acrolein to allyl alcohol.

6 EXAMPLE 4 In Table 4, the influence of the heat-treating temperature on activity and selectivity of the catalyst is shown in the hydrogenation of crotonaldehyde to crotyl alcohol. The heat-treatments in this example are effected for 3 hours under a hydrogen stream.

EXAMPLE 5 Although the employment of the Raney copper cadmium catalyst prepared from varied composition of the alloy in each example obviates the influence of the proportion of catalyst metals in the alloy to activity and selectivity of the catalyst, Table 5 further clarifies the results Where the proportions of copper and cadmium are changed (at the constant amount of aluminum) in the alloy in the hydrogenation of crotonaldehyde to crotyl alcohol. Also, Table 5 reflects the use of a small proportion of aluminum in the catalyst.

TABLE 2 Reaction Reaction Liquid Conver- Catalyst pressure, temperaspace sion (per- Yield (kgJcmfl ture 0.) Velocity cent) (percent) abs.) (l./1. hr.)

1 175 0. 63 2. 9 26. 6 Precipitated binary catalyst CuzCd2Dia-tm. earth 53.3:18.7:28.0 1 225 0. 63 8.2 76. 0 5 175 0.53 12.0 70. 2 5 225 0. 58 31. 7 73. 4

Catalyst Ternary Alloy (wt. percent) Composition (wt. percent) CuzCdzAl Surface Cu:Cd-Al area (rnJ/ 1 175 0. 66 12. 9 75. 1 47.2=7.0=45.s 7152;115:125 heated at 275 0. for 3 hrs. under Hg.-. 27. 6 g 5 225 0. 50 68. 1 81. 2

TABLE 3 Reaction Reaction Liquid Con- Catalyst Pressure temperaspace velversion Yield (kgJcm. ture C.) ocity (percent) (percent) abs.) (l./l. hr)

Precipitated binary catalyst Cu:Cd:Diat0m. earth 53.3:18.7:28.0 1 175 0.60 2. 1 4, 5 1 225 0. 59 3. 8 14. 0 Catalyst Ternary alloy Cu: CdzAl Composition heated at 275 C. for 3 hrs. under H2 (wt. Surface percent) Cu: Cd:Al area TABLE 4 Catalyst Catalyst Reaction Reaction Liquid space Conversion Yield Ternary alloy Temperature pressure temperature velocity (percent) (percent) (wt. percent) Composition Surface of heat (kg/cm. abs.) C.) (l./l. hr.)

Cu: CdzAl (wt. percent) area treatment,

CuzCdzAl (rufi/g.) C.

I 225 1 225 0. 64 98.5 5.3 54.2.3.5.423 79.0.5.l.1a.9 18. 6 i g3 49' 1 56' 7 31.6 81.2 38.7.2.1.59.2 .o.o.3.s.2e.2 3s. 2 325 1 225 0 69 0 m 3 TABLE 5 Catalyst Liquid Alloy Catalyst Reaction Reaction space Con- Yield Composition pressure temperature velocity version (percent) (wt. percent) Composition Surface Heat treatment (kg./cm. abs.) C.) (l./l. hr.) (percent) Cu: CdzAl (wt. percent) area CuzCdzAl (mfllg) 4?.9:4.1:50.g 7ggrggziggun g 0.38 31.0 84.3 4. "0. 7..: o 0. 0 98.0 9.1 72. 0105:1717. a1. 0 Pleated at 275 3 1115' mde? 3 225 0.55 29.6 81.6 71.1:7. 1:21. 8 8. 0 3 225 0.60 32. 1 78. 8

7 EXAMPLE 6 In Table 6, the heat-treatment under a hydrogen stream is compared with that under a nitrogen stream for the hydrogenation of crotonaldehyde to crotyl alcohol.

8 Regarding zinc-chromium binary catalysts, many results have been reported, in addition to those of Komori, in British Patent 806,619, Masloboino-Zhirovaya Prom, vol. 25, No. 10, page 25 (1959) and Tr. Vses. Nauchn.-

TABLE 6 Catalyst Liquid Catalyst Reaction Reaction space Conversion Yield Alloy Composipressure temperature velocity (percent) (percent) tion (wt. percent) Composition Surface Heat treatment (kg/cm. abs.) C.) (l./l. hr.)

Cu: CdzAl (wt. percent) Area Cu:Cd:Al (mi/g.)

{;2 s;;2i:::;a;;; i 8:22 222 a:

EXAMPLE 7 1r Issled. Inst. Zhirov, No. 20, page 216 (1960). Further,

In Table 7, the results of the production of Z-ethylhexen 2 ol 1 by hydrogenation of 2 ethyl hexen-2- al-l using the present Raney catalyst are shown.

there are reports on zinc-vanadium and cadmium-vanadium binary catalysts (German Patent 865,741).

However, with prior catalysts it is ordinarily necessary TABLE 7 Catalyst Liquid Catalyst Reaction Reaction space Conversion Yield Alloy Composipressure temperature velocity (percent) (percent) tion (wt. percent) Composition Surface Heat treatment (kg/cm. abs.) C.) (1.,1. hr)

CuzCdzAl (wt. percent) Area CllzCdzAl (HIP/g a 1 245 0.86 31. 68. 1 47.2.7.0.458 71.5.10.6.17.9 26. 0 275 0., 3 his. H2 3 245 68 60. 2 35.5

EXAMPLE 8 to adopt reaction temperatures of from 300 to 330 C. in

In Table 8, the results of the production of 2-methyl- 30 pentan-2-ol-4 by hydrogenation of mesityloxide using the present Raney catalyst are shown.

addition to using the catalyst in an amount of about 10 to based on the weight of the reactants when the reaction is a catalyst-suspension type liquid phase reaction.

TABLE 8 Catalyst Liquid Catalyst Reaction Reaction space Conversion Yield Alloy Composipressure temperature velocity (percent) (percent) tion (wt. percent) Composition Surface Heat treatment (kg/cm. abs.) C.) (l./1. hr.)

CuzCdzAl (wt. percent) Area CuzCdzAl /g 50.9:5.1;44.0 74.9:7.5:17.6- 21.0 275 0., 3 hrs. H2 g 352 8:

The catalyst of this invention also exhibits excellent activity and selectivity in the production of unsaturated higher aliphatic alcohols by hydrogenation of unsaturated fatty acids or unsaturated fatty acid esters, and has prominent properties as an industrial catalyst in view of the catalyst life and the easy recovery from reaction products.

Also according to the present invention unsaturated higher, e.g. C to C aliphatic alcohols are produced economically and in high yield from fatty acids or fatty acid esters having ethylenically unsaturated groups, utilizing the excellent properties of the afore-said catalyst as an industrial catalyst.

The production of unsaturated higher aliphatic alcohols In Japanese Patent No. 136,030 a catalyst containing copper is used in producing unsaturated higher aliphatic alcohols from unsaturated fatty acids or esters thereof. The catalyst is supported on a carrier, such as diatomaceous earth, the copper and cadmium being converted into the form of hydroxides by alkali treatment of mineral acid salts thereof, and then washing and drying the resultant. As an example of using a copper-chromite catalyst in combination with cadmium, Lauer et al. reported the reduction of Egyptian cottonseed oil at 350 C., using 10% of a cadmium-modified copper chromite catalyst. [Osterr. chem.-Ztg., vol. 56, page 255 (1955)].

Also, Moreno et al. effected this kind of hydrogenation by hydrogenation of fatty acids or fatty acid esters having at 265 C. by using 10% copper-chromite catalyst in comunsaturated groups was reported by Sauer and Adkins in bination with 3.75% cadmium carbonate. [Grass y J. Am. Chem Soc., vol. 59, page 1 (1937) and unsatu- Aceites (Seville, Spain), vol. 9, page (1958)]. Dutch rated higher aliphatic alcohols were obtained from unsatu- Patent 83,379 describes the preparation of unsaturated rated fatty acid esters by use of mixed metal oxide catahigher aliphatic alcohols from corresponding unsaturated lysts. The catalyst was employed in a large amount (about 60 fatty acids at reaction temperatures of 280 C. to 300 C. 50% by weight based on the starting material) and the by using a catalyst comprising 60 to 90% of copper soap reaction time required was 7 to 11 hours. Much research and 40 to 10% of cadmium soap. In addition, regarding has since been conducted on this kind of hydrogenation. the production of unsaturated higher aliphatic alcohols Using metals other than copper as catalysts, the most defrom unsaturated fatty acids by use of said copper-cadtailed research is that of Komori, who compared catalyst mium soap catalyst, the results of detailed research have abilities of various mixed metal oxide catalysts and obbeen announced [Chim. et Ind. (Paris);-- vol. 83, page served that particularly efiective catalysts are zinc-chro- 875 (1960)]. v

mium oxide [Kogyo Kagaku Zasshi, vol. 41, page 419 When this kind of hydrogenation is effected by use of a (1938)] and iron-chromium oxide [Kogyo Kagaku solid catalyst, there have conventionally been required a Zasshi, vol. 43, page 910 (1940)]. Sasazaki recognized high temperature and a large amount of the catalyst based that a zinc powder is also effective on this kind of hydrogenation [Nihon Nogei Kagaku Kaishi, vol. 15, page 531 1939)], and Kobashi et al. reported that zinc-aluminum oxides and iron-zinc oxides are excellent catalysts [Kogyo Kagaku Kaishi, vol. 54, page 581 (1951)].

on the weight of the reactants. However, the reaction at high temperatures of fatty acids or fatty acid esters having unsaturated groups necessarily causes undesirable side reactions, such as the dehydration or polymerization of reactants, whereby the reaction yield is markedly lowered.

Also, the use of a large amount of catalyst, based on the weight of reactants, is disadvantageous from an industrial point of view. Moreover, the metal oxide catalysts or supported catalysts are diflicultly separable from reaction products, when used in catalystsuspension-type liquid phase reactions. Great pains are required to recover the catalysts. Metallic soap catalysts appear to permit lower reaction temperatures and lesser amounts of catalyst, but suffer from many industrial drawbacks, since it is diflicult to reuse them.

The present Raney copper cadmium catalyst makes possible the production of unsaturated higher aliphatic alcohols in high yields in an extremely short period at a reaction temperature of 250 to 280 C., even though the catalyst is employed, when a catalyst-suspension type liquid phase reaction is adopted, is as small an amount as 3 to 5% based on the weight of reactants. Also, said catalyst suffers little from lowering in activity by repeated use, as shown in Example 13, and further has excellent properties as an industrial catalyst in that, when used in a catalystsuspension type liquid phase reaction, it is separable from the reaction product with extreme ease (see Example 14).

The present invention is further illustrated with reference to the following examples, wherein the analytical values of each reaction product are measured on substance obtained by thoroughly saponifying the product after the removal of the catalyst, treating the saponified product with hydrochloric acid, washing the treated substance with water and then topping the same under reduced pressure to remove methanol or butanol completely.

EXAMPLE 9 In an electric furnace, heat a graphite crucible to about 700 C. Melt 180 g. (grams) of an aluminum-copper (1:1 by weight ratio) binary alloy lump in the crucible. Subsequently, charge g. of a cadmium-copper (1:1 by weight ratio) binary alloy lump in the crucible, while thoroughly stirring the content. Discharge the resulting alloy on a floor while stirring with a silica rod. Immediately cool said resulting alloy rapidly with water and crush into a grain size of 200 to 250 mesh. The resulting alloy has a com- 10 (wt. percent CuzCdzA-l) of 88.0:8.6:3.2; and a surface area (m. g.) of 25.0. Fill a quartz tube with the catalyst grains and heat said grains at 300 C. for 3 hours in a hydrogen current.

Add 3 g. of the above catalyst to g. of methyl oleate (iodine number: 89.1, saponification value: 192.3, acid number: 0) Charge the resulting mixture in a shaking-type autoclave having an inner volume of 1 1. (liter). Shake in the autoclave for 120 minutes at 260 C. under an initial hydrogen pressure of 120 kg./cm. (kilograms per square centimeter) at 20 C., and cool. The reaction product has an iodine number of 72.8, an acid number of 54.1 and a hydroxyl value of 160.0. The hydroxyl value is the weight (mg.) of caustic potassium required for neutralizing acetic acid formed by decomposing the acetylated product obtained by acetylating 1 g. of the sample.

EXAMPLE 10 Add 5 g. of the catalyst obtained by the method of Example 9 to 100 g. of butyl oleate (iodine number: 77.2; saponification value: 170.1; acid number: 0.8). React the resulting mixture in the autoclave of Example 9 at 260 C. for 150 minutes under an initial hydrogen pressure of 130 l g./cm. at 20 C., and then cool. The reaction product has an iodine number of 75.0, an acid number of 55.2, and a hydroxyl value of 155.0.

EXAMPLE 1 1 The activity on butyl oleate of the present Raney catalyst is compared with that of a copper-cadmium binary catalyst carried by diatomaceous earth. The results are shown in Table 9.

The copper-cadmium binary catalyst carried by diatomaceous earth is prepared conventionally, i.e., by dissolving given amounts of copper nitrate and cadmium nitrate in water to form an aqueous solution, coprecipitating from said aqueous solution copper hydroxide and cadmium hydroxide by use of caustic soda, mixing said hydroxides with a carrier, drying the resulting mixture at to C., calcining the dried mixture in air at 400 C. for 4 hours, and then reducing the calcined mixture at 300 C. for 3 hours.

TABLE 9 [Butyl oleate.-Analytical values=I0dine number: 77.2; saponification value: 170.1; Acid number: 0.8; Amount charged: 100 g.]

Initial Analytical value of Catalyst Reaction Reaction hydrogen reaction product- Catalyst amount tempertime pressure (g) a ture (min) at 26 C. Iodine Acid Hydroxyl V C.) (kg/em?) number number value Binary Catalyst prepared by precipitating method (Composition by wt. Cu:Cd:diat0maceous earth=53.3:18.7: 28.0) 10 260 150 100 86. 9 165. 1 40. 3 Raney catalyst shown in Example 9 l 260 150 100 75. 4 57. 8 153. 1

position (wt. percent Cu:Cd:Al) of 50.0:5.0:45 .0. Submerge 10g. of the thus obtained alloy grains in 1000 g. of 10% aqueous caustic soda solution at 30 C. for 15 minutes. Upon the alkali-treatment, most of the aluminum is dissolved out.

After the treatment, discard the alkali liquid and wash the thus obtained catalyst grains with water until the wash The autoclave employed was the same as in Example 9.

EXAMPLE 12 By use of the catalyst obtained in Example 9, oleic acid, olive oil and methyl ester prepared from rice oil, respectively, are hydrogenated. The adopted reaction conditions and the obtained reaction products are summarized in water is neutral. The resulting catalyst has a composition 60 Table 10.

TABLE 10 Feed I Initial Analytical values of Catalyst Reaction Reaction hydrogen reaction productamount temperature time pressure Charged (g.) 0.) (min.) at 20 C Iodine Acid Hydroxyl N ame and analytical anzognt (kgJcm number number value Oleic acid:

Iodine number 71. 2 saponification value 206. 4 100 8 280 180 74. 6 55. 0 155. 6 Acid number- 205. 4 Olive oil:

Iodine number 78. 7 saponification value. 192. 1 100 10 260 120 71. 5 87. 2 120. 9 Acid number 2. 5 Rice oil methyl ester:

Iodine number 122. 4 saponification valu 189. 4 100 5 250 100 120 78. 1 61. 3 149. 2 Acid number O The present Raney catalyst may be used repeatedly. Test results are shown in Table 11. The test is carried out as follows:

Add 5 g. of catalyst obtained in Example 9 to 100 g. of methyl oleate (iodine number: 89.1; saponification value: 192.3; acid number: React the resulting mixture in the autoclave of Example 9 at 260 C. for 100 minutes under an initial hydrogen pressure of 100 kg./cm. at 20 C. After the reaction, separate the catalyst from the reaction mixture and recharge the autoclave with the used catalyst and a fresh sample (100 g.) of the methyl oleate. Repeat the preceding reaction under the stated conditions. Repeat the same operations thereafter for a total of five times. All the reaction conditions after the second time are the same as those of the first time.

TABLE 11 Analytical value of reaction product Time of repeated use Iodine Acid number Hydrexyl number value EXAMPLE 14 in order to examine the degree of separation of catalyst from reaction product, remove the reaction product (obtained by the catalyst having been repeatedly used for three times in Example 13) from the autoclave and vigorously stir again at 50 C. 2 minutes after the discontinuation of stirring, decant the supernatant. The amount of catalyst incorporated in said supernatant is 0.1 g. That is, 93% of the total amount (5 g. of catalyst) present in said reaction product is removable with extreme ease merely by decantation.

The preceding examples were directed to the catalyst embodying the first aspect of this invention. The catalyst embodying the second aspect of this invention could also be used in the foregoing examples wherein the catalytic activity is set forth. The following examples are directed to the catalyst of the second aspect of this invention.

EXAMPLE 15 A graphite crucible was heated at about a temperature 1 of 700 C. in an electric furnace. 194 g. of two component alloy mass consisting of aluminum and copper in a proportion of 50:47 by Weight were melted in this crucible. Then 6 g. of two component alloy mass consisting of cadmium and copper in a proportion of 1:1

by weight was introduced therein while stirring. Whilebeing stirred well by a bar of silica, the content Was discharged on a floor, immediately cooled by water and after being cooled, crushed to 200 to 250 mesh.

10 g. of the resulting alloy was treated with 1 kg. of 10 percent aqueous solution of sodium hydroxide at a temperature of 30 C. for minutes. After this treatment, the alkaline solution was discarded, and the alloy was washed with water until washed solution becomes neutral. The washed alloy was filled in a quartz tube and treated in a hydrogen atmosphere at a temperature of 290 C. for 3 hours.

5 g. of the above-mentioned catalyst was added to 100 g. of butyl oleate (iodine value 76.8, saponification value 1682; and acid value 0.1). This mixture was charged in an autoclave having an internal volume of 1 liter and equipped with a stirrer and allowed to react at an initial hydrogen pressure of 130 kg./cm. (at C.), at a temperature of 265 C. for 150 minutes. The analytical values of the product formed were as follows:

iodine value 70.3, acid value 49.8, hydroxyl value 157.0. The hydroxy value was expressed as milligrams of potassium hydroxide required to neutralize acetic acid produced by decomposing 1 gram of the acetylated product.

EXAMPLE 16 8 g. of the catalyst obtained in Example 15 was added to 100 g. of olefic acid (iodine value 72.0, saponification value 207.6 and acid value 205.5). The mixture was allowed to react in the autoclave of Example 15 at an initial hydrogen pressure of 140 kg./cm. (at 20 C.) at a temperature of 280 C. for 150 minutes. The analytical values of the product measured after being taken out and treated as in Example 15 were as follows: iodine value 68, acid value 65.1, and hydroxyl value 139.8.

EXAMPLE 17 198.4 g. of a two component alloy mass consisting of aluminum and copper in a proportion of 34:15.6 by weight and 1.6 g. of a two component alloy mass consisting of cadmium and copper in a proportion of 1:1 were melted in a crucible by the method set forth in Example 15, While being stirred well, discharged on a floor, immediately cooled by water and after being cooled, crushed into lumps of 3 to 5 millimeters.

g. of the crushed alloy Was treated in 700 g. of 10 percent sodium hydroxide solution at a temperature ranging from 100 to 101 C. for 3 hours and washed sufficiently with water after discarding the alkaline solution. The treated alloy was added to the middle of a reaction tube made of SUS (trade name of a Japanese stainless steel manufacturer) and having an internal diameter of 18 mm. and length of 400 mm. and subjected to heat treatment at a temperature of 275 C. for 3 hours under a hydrogen atmosphere. The so-obtained catalyst was used for hydrogenation of 6-methyl-A -tetrahydro benzaldehyde. The results of this hydrogenation is shown in the following Table 12.

TAB LE 12 Reaction temperature 0.)

Liquid Converspace sion Yield velocity (percent) (percent) (l./l. hr.)

Reaction pressure (kg. lcm. abs.)

Experiment Number 1 mol ratio of 1:12. The composition of the product was calculated by simultaneous use of gas chromatography and chemical analysis. The conversion indicated in the table is the percentage by weight of 6-methyl-A -tetrahydrobenzaldehyde converted to other substances to that fed to the reaction tube. Yield is the percentage of weight of 6-methy1-A -tetrahydrobenzyl alcohol to converted substance.

Various changes may be made in the processes and in the catalysts without departing from the spirit or the scope of the invention or sacrificing its material advantages, the processes and catalysts hereinbefore described being merely illustrative of preferred embodiments of the invention.

What is claimed is:

1. A method for the preparation of an activated Raneytype ternary alloy catalyst which comprises melting a mixture of aluminum, copper and cadmium, said mixture containing from 30 to 60 percent by weight of aluminum with from 4 to 15 percent by weight of the remainder of the mixture being cadmium and the balance being copper, to form a molten ternary alloy, solidifying the alloy by cooling same, pulverizing the solidified alloy, submerging the pulverized alloy in aqueous alkali solution, waterwashing alkali from the alkali-treated alloy, heating the water-washed alloy at a temperature from 250 to 350 C. under a hydrogen gas stream.

2. A method for the preparation of an activated Raneytype ternary alloy catalyst which comprises melting a mixture of aluminum, copper and cadmium, said mixture containing from 30 to 60 percent by weight of aluminum with from 4 to 15 percent by weight of the remainder of the mixture being cadmium and the balance being copper, to form a. molten ternary alloy, solidifying the alloy by cooling same, pulverizing the solidified alloy, submerging the pulverized alloy in aqueous alkali solution, water-washing alkali from the alkali-treated alloy, heating the waterwashed alloy at a temperature from 250 to 350 C. in an inert atmosphere.

3. Activated Raney-type ternary alloy catalyst produced by heating a Raney-type ternary alloy catalyst consisting essentially of aluminum, cadmium and copper, the weight percent of aluminum being from 1 to 50 percent and the weight of cadmium being 4 to 15 percent of the remainder of the weight of the catalyst and the balance being copper, to a temperature from 250 to 350 C. in a stream of hydrogen.

4. A process of activating Raney-type ternary alloy catalyst consisting essentially of aluminum, cadmium and copper, which process consists essentially of heating the catalyst at a temperature from 250 to 350 C. in a stream of hydrogen gas.

5. A process of activating Raney-type ternary alloy catalyst consisting essentially of aluminum, cadmium and copper, which process consists essentially of heating the catalyst at a temperature from 25 to 350 C. in a stream of nitrogen gas.

6. A process of activating Raney-type ternary alloy catalyst consisting essentially of aluminum, cadmium and copper, which process consists essentially of heating the catalyst at a temperature from 250 to 350 C. in an inert atmosphere.

7. A method for the preparation of an activated Raneytype ternary alloy catalyst which comprises melting a mixture of aluminum, copper and cadmium, said mixture containing from 30 to percent by weight of aluminum with from 1 to less than 4 percent by weight of the remainder of the mixture being cadmium and the balance being copper, to form a molten ternary alloy, solidifying the alloy by cooling same, pulverizing the solidified alloy, submerging the pulverized alloy in aqueous alkali solution, water-washing alkali from the alkali-treated alloy, heating the water-washed alloy at a temperature from 250 to 350 C. under a hydrogen gas stream.

8. A method for the preparation of an activated Raneytype ternary alloy catalyst which comprises melting a mixture of aluminum, copper and cadmium, said mixture containing from 30 to 70 percent by weight of aluminum with from 1 to less than 4 percent by weight of the remainder of the mixture being cadmium and the balance being cop per, to form a molten ternary alloy, solidifying the alloy by cooling same, pulverizing the solidified alloy, submerging the pulverized alloy in aqueous alkali solution, water-washing alkali from the alkali-treated alloy, heating the water-washed alloy at a temperature from 250 to 350 C. in an inert atmosphere.

References Cited UNITED STATES PATENTS 1,658,757 2/1928 Bernhoeft -l39 2,026,551 1/1936 Fink 75--139 2,074,528 3/1937 Andrews et al. 260638 2,332,834 10/1943 Van Schuckmann 260-638 2,504,497 4/1950 Charles et al 252463 2,604,455 7/1952 Reynolds et al. 252463 X 2,763,696 9/1956 Finch et al. 252475 X FOREIGN PATENTS 611,987 11/1948 Great Britain.

DANlEL E. WYMAN, Primary Examiner.

P. E. KONOPKA, Assistant Examiner. 

